• 제목/요약/키워드: $Bi_3O_4Cl$

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류천(柳川) 창연광상(蒼鉛鑛床) 광석광물(鑛石鑛物), 유체포유물(流體包有物) 및 안정동위원소(安定同位元素) (Ore Minerals, Fluid Inclusions and Stable Isotopes of the Yucheon Bismuth Deposits, Korea)

  • 이현구;유봉철;김상중
    • 자원환경지질
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    • 제29권2호
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    • pp.139-150
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    • 1996
  • The Yucheon Bi deposits at Cheongha, Gyeongsangbugdo, is of a middle Paleogene (49 Ma) vein type, and is hosted in sandstone and shale of Banyawal formation in Cretaceous age. Based on mineral paragenesis, vein structure and mineral assemblages, two minera1ization stages were distinguished. The stage I consists of quartz with small amount of chlorite, pyrite, epidote, hal1oysite, vermiculite, serpentine and rutile associated with sericitization. The stage II is characterized by Bi minera1ization such as bismuthinite, Bi-Cu-Pb-S mineral, tetradymite, native gold, pyrite, pyrrhotite, arsenopyrite, wolframite, rutile, hematite, sphalerite, chalcopyrite, galena with alteration of sericite, chlorite, K-feldspar, albite and epidote. Fluid inclusion data indicate that fluid temperature and NaCl equivalent wt.% salinity range from 431 to $150^{\circ}C$ and from 19.2 to 0.18wt.% in the stage II. Evidence of boiling during the base-metal minera1ization indicates pressures 241 to 260 bars. Sulfur fugacity($-log\;f_{S2}$) deduced by mineral assemblages and compositions ranges from 5.1 to 5.7atm in early stage, from > 8.4 atm in middle stage and from 13.5 to 19.3 atm in late stage. It suggests that complex histories of progressive coo1ing, dilution and boiling were occurred by the mixing of the fluids. The ${\delta}^{34}S$, ${\delta}^{18}O$ and ${\delta}D$ data range from 2.5 to 3.9%, -0.5 to -4.1% and -29.7 to -47%, respectively. It indicated that hydrothermal fluids may be magmatic origin with boiling and mixing of meteoric water increasing paragenetic time.

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Tris(tetraethylammnnium) [bis(trimetaphosphate $\kappa^3O, O^', O^{"}$)] Vamdate(3-),$[V(P_3O_9)_2](NC_8H_{20})_3$,의 두가지 가능한 공간군 (Two Possible Space Groups of Ttis(tekaethylammonium) [bis(trimetaphosphate $\kappa^3O, O^', O^{"}$)] Vanadate(3-),$[V(P_3O_9)_2](NC_8H_{20})3$)

  • 서일환;이진호
    • 한국결정학회지
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    • 제5권1호
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    • pp.1-6
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    • 1994
  • 화합물 VP6N3018C243H60의 두 가지 가능한 공간군은 PT,a=14.O22(1), b=12.644(2), c=12.640(1)A, a=80.38(1), β=102.12(1), y =102.16(1), V=2124.1A3, Z=2, u=0.47cm-1,d==1.46g/cm3, Fo>4c IfoI인 3350윤의 독립반사강도에 대하여 R=0.083 과 C2/c, a=19.32(2), b=16.32(2), c=14.02(1)A, β= 105.98(5), V=4348.2A3, Z=4, Fo>4o IFoI인 1590개의 독립반사강도에 대하여 R=0.083 이다. 주간군 Pi의 경우 단위포내에 두 분자가 있는데 각 분자내의 바나둠 원자가 특수치치에 있어 중심대칭에 의하여 한 분자를 이루고 있으므로 단위포내의 비대칭단위는 두개의 bis(timetalhosphate)vanadate 반분자와 3개의 tetraethylammDnium분자로 되어있다. 공문군 C2/c의 경우 bis(trimetaphosphate)vanadate 한분자의 vanadium 원자가 중심대1칭을 갖는 변광단동치에 있으며, 3개의 tetrethylammonium 분자중 한 분자내의 CL2, N2, C25 원자들을 2-회회전대칭축이 지나므로 bis(trimetaphosphate)vanadate 반분자와 tetraethylammonium 3/2 분자가 비대칭단위를 이루고 있다. 두 경우 공히 vanadium원자를 배위하고 있는 6개의 산소원자가 8함체를 이루며 nitrogen원자와 결합하고 있는 4개의 carbon 원자들은 모두 disorder되어 있어 nitrogen원자의 주권에 있는 8개의 carbon 원자들은 불규칙한 12면체를 이루고 있다.

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Sesquiterpenoids Bioconversion Analysis by Wood Rot Fungi

  • Lee, Su-Yeon;Ryu, Sun-Hwa;Choi, In-Gyu;Kim, Myungkil
    • 한국균학회소식:학술대회논문집
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    • 한국균학회 2016년도 춘계학술대회 및 임시총회
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    • pp.19-20
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    • 2016
  • Sesquiterpenoids are defined as $C_{15}$ compounds derived from farnesyl pyrophosphate (FPP), and their complex structures are found in the tissue of many diverse plants (Degenhardt et al. 2009). FPP's long chain length and additional double bond enables its conversion to a huge range of mono-, di-, and tri-cyclic structures. A number of cyclic sesquiterpenes with alcohol, aldehyde, and ketone derivatives have key biological and medicinal properties (Fraga 1999). Fungi, such as the wood-rotting Polyporus brumalis, are excellent sources of pharmaceutically interesting natural products such as sesquiterpenoids. In this study, we investigated the biosynthesis of P. brumalis sesquiterpenoids on modified medium. Fungal suspensions of 11 white rot species were inoculated in modified medium containing $C_6H_{12}O_6$, $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ for 20 days. Cultivation was stopped by solvent extraction via separation of the mycelium. The metabolites were identified as follows: propionic acid (1), mevalonic acid lactone (2), ${\beta}$-eudesmane (3), and ${\beta}$-eudesmol (4), respectively (Figure 1). The main peaks of ${\beta}$-eudesmane and ${\beta}$-eudesmol, which were indicative of sesquiterpene structures, were consistently detected for 5, 7, 12, and 15 days These results demonstrated the existence of terpene metabolism in the mycelium of P. brumalis. Polyporus spp. are known to generate flavor components such as methyl 2,4-dihydroxy-3,6-dimethyl benzoate; 2-hydroxy-4-methoxy-6-methyl benzoic acid; 3-hydroxy-5-methyl phenol; and 3-methoxy-2,5-dimethyl phenol in submerged cultures (Hoffmann and Esser 1978). Drimanes of sesquiterpenes were reported as metabolites from P. arcularius and shown to exhibit antimicrobial activity against Gram-positive bacteria such as Staphylococcus aureus (Fleck et al. 1996). The main metabolites of P. brumalis, ${\beta}$-Eudesmol and ${\beta}$-eudesmane, were categorized as eudesmane-type sesquiterpene structures. The eudesmane skeleton could be biosynthesized from FPP-derived IPP, and approximately 1,000 structures have been identified in plants as essential oils. The biosynthesis of eudesmol from P. brumalis may thus be an important tool for the production of useful natural compounds as presumed from its identified potent bioactivity in plants. Essential oils comprising eudesmane-type sesquiterpenoids have been previously and extensively researched (Wu et al. 2006). ${\beta}$-Eudesmol is a well-known and important eudesmane alcohol with an anticholinergic effect in the vascular endothelium (Tsuneki et al. 2005). Additionally, recent studies demonstrated that ${\beta}$-eudesmol acts as a channel blocker for nicotinic acetylcholine receptors at the neuromuscular junction, and it can inhibit angiogenesis in vitro and in vivo by blocking the mitogen-activated protein kinase (MAPK) signaling pathway (Seo et al. 2011). Variation of nutrients was conducted to determine an optimum condition for the biosynthesis of sesquiterpenes by P. brumalis. Genes encoding terpene synthases, which are crucial to the terpene synthesis pathway, generally respond to environmental factors such as pH, temperature, and available nutrients (Hoffmeister and Keller 2007, Yu and Keller 2005). Calvo et al. described the effect of major nutrients, carbon and nitrogen, on the synthesis of secondary metabolites (Calvo et al. 2002). P. brumalis did not prefer to synthesize sesquiterpenes under all growth conditions. Results of differences in metabolites observed in P. brumalis grown in PDB and modified medium highlighted the potential effect inorganic sources such as $C_4H_{12}N_2O_6$, $KH_2PO_4$, $MgSO_4$, and $CaCl_2$ on sesquiterpene synthesis. ${\beta}$-eudesmol was apparent during cultivation except for when P. brumalis was grown on $MgSO_4$-free medium. These results demonstrated that $MgSO_4$ can specifically control the biosynthesis of ${\beta}$-eudesmol. Magnesium has been reported as a cofactor that binds to sesquiterpene synthase (Agger et al. 2008). Specifically, the $Mg^{2+}$ ions bind to two conserved metal-binding motifs. These metal ions complex to the substrate pyrophosphate, thereby promoting the ionization of the leaving groups of FPP and resulting in the generation of a highly reactive allylic cation. Effect of magnesium source on the sesquiterpene biosynthesis was also identified via analysis of the concentration of total carbohydrates. Our current study offered further insight that fungal sesquiterpene biosynthesis can be controlled by nutrients. To profile the metabolites of P. brumalis, the cultures were extracted based on the growth curve. Despite metabolites produced during mycelia growth, there was difficulty in detecting significant changes in metabolite production, especially those at low concentrations. These compounds may be of interest in understanding their synthetic mechanisms in P. brumalis. The synthesis of terpene compounds began during the growth phase at day 9. Sesquiterpene synthesis occurred after growth was complete. At day 9, drimenol, farnesol, and mevalonic lactone (or mevalonic acid lactone) were identified. Mevalonic acid lactone is the precursor of the mevalonic pathway, and particularly, it is a precursor for a number of biologically important lipids, including cholesterol hormones (Buckley et al. 2002). Farnesol is the precursor of sesquiterpenoids. Drimenol compounds, bi-cyclic-sesquiterpene alcohols, can be synthesized from trans-trans farnesol via cyclization and rearrangement (Polovinka et al. 1994). They have also been identified in the basidiomycota Lentinus lepideus as secondary metabolites. After 12 days in the growth phase, ${\beta}$-elemene caryophyllene, ${\delta}$-cadiene, and eudesmane were detected with ${\beta}$-eudesmol. The data showed the synthesis of sesquiterpene hydrocarbons with bi-cyclic structures. These compounds can be synthesized from FPP by cyclization. Cyclic terpenoids are synthesized through the formation of a carbon skeleton from linear precursors by terpene cyclase, which is followed by chemical modification by oxidation, reduction, methylation, etc. Sesquiterpene cyclase is a key branch-point enzyme that catalyzes the complex intermolecular cyclization of the linear prenyl diphosphate into cyclic hydrocarbons (Toyomasu et al. 2007). After 20 days in stationary phase, the oxygenated structures eudesmol, elemol, and caryophyllene oxide were detected. Thus, after growth, sesquiterpenes were identified. Per these results, we showed that terpene metabolism in wood-rotting fungi occurs in the stationary phase. We also showed that such metabolism can be controlled by magnesium supplementation in the growth medium. In conclusion, we identified P. brumalis as a wood-rotting fungus that can produce sesquiterpenes. To mechanistically understand eudesmane-type sesquiterpene biosynthesis in P. brumalis, further research into the genes regulating the dynamics of such biosynthesis is warranted.

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다이아튜림 내에 부존한 녹동 비소-아연광상의 광석광물, 유체포유물, 유황-탄소-산소 동위원소 : 광화용액의 특성과 진화 (Ore Minerals, Fluid Inclusions, and Isotopic(S.C.O) Compositions in the Diatreme-Hosted Nokdong As-Zn Deposit, Southeastern Korea: The Character and Evolution of the Hydrothermal Fluids)

  • 박기화;박희인;;최석원
    • 자원환경지질
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    • 제24권2호
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    • pp.131-150
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    • 1991
  • 시간적-공간적으로 가대리 화강암과 관련되어 형성된 월성 다이아튜림은 천수에서 유래된 용액에 의해 광화되어 있다. 이 광상에서 광석광물은 황철석, 유비철석, 섬아연석이 대부분이고 극소량의 자철석, 자류철석, 황동석, 석석과 Pb-Sb-Bi-Ag 계의 광문이 있다. 유체포유물, 유비철석에서의 비소함량과 섬아연석의 철 함량에 의해 계산된 비소-아연 광화 온도는 약 $350^{\circ}C$에 이르며, 염농도는 0.8에서 4.1 equ. wt % NaCl이다. 공생을 이루는 황철석-자류철석-유비철석은 $H_2S$ 주요 환원황으로 작용했으며, $300^{\circ}C$에서 산출한 광황용액은 $10^{34.5}$ < ${alpha}_{O_2}$ < $10^{-3}$, $10^{-11}$ < $f_{S_2}$ < $10^{-8}$, $10^{-2.4}$ < ${alpha}_{H_2S}$ < $10^{-1.6}$이고 pH는 견운모 안정범위인 5.2이하이다. 유화광물의 유황동위 원소비는 1.8에서 5.5%로서 유황은 마그마에서 기원되었다. 광화대에서의 탄산염 광물의 탄소 동위 원소비는 -7.8에서 -11.6%이고 산소 동위원소 값은 천수의 유입이 있었음을 의미한다. 지화학적 자료로 보아 광화용액은 마그마에 천수가 유입되어 마그마 열원의 영향하에 지하 심부 순환관정을 거쳐 형성된 것으로 해석된다.

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